Isocyanophenyl carbamates

ABSTRACT

Novel isocyanophenyl carbamates of the formula   WHEREIN X1 and X2 are each oxygen or sulfur; R1 and R2 are each hydrogen, alkyl (C1-C4), aryl, substituted aryl, or cycloaliphatic; R3 is selected from the group consisting of alkyl (C1-C6), alkoxy, allyl, methylenedioxy, haloalkyl, propargyloxy and allyloxy; N IS AN INTEGER FROM 0 TO 4 INCLUSIVE; AND A is phenyl or naphthyl. These compounds are useful as insecticides and acaricides.

[ Jan. 28, 1975 i 1 ISOCYANOPHENYL CARBAMATES [75] Inventor: David L. Booth, Crystal Lake, ill

[73] Assignee: fifirton-Norwich Products, Inc.,

Chicago, ill.

22 Filed: Aug. 1, 1972 211 Appl.No.:277,053

[52] U.S. Cl 260/465 1), 260/340.5, 260/455 A,

Primary Examiner-Lewis Gotts Assislunr Examiner-Dolph H. Torrence Attorney, Agent, or Firm.lack Axelrood [57] ABSTRACT Novel isocyanophenyl carbamates of the formula 2 ll )1 X c l z (R A NC wherein X and X are each oxygen or sulfur;

R and R are each hydrogen, alkyl (CR-C aryl,

substituted aryl, or cycloaliphatic;

R is selected from the group consisting of alkyl ('C,C alkoxy, allyl, methylenedioxy, haloulkyl, propargyloxy and allyloxy;

n is an integer from 0 to 4 inclusive; and

A is phenyl or naphthyl.

These compounds are useful as insecticides and acuricides.

10 Claims, N0 Drawings HSOCYANOPHENYL CARBAMATES BACKGROUND OF THE INVENTlON 1. Field of the Invention This invention relates to novel isocyanophenyl carbamates and their use as insecticides and acaricides.

2. Description of the Prior Art It is known that bicyclic and tricyclic isonitriles display pesticidal activity (See US. Pat. No. 3,419,526); that aliphatic, cycloaliphatic and aralkyl isonitriles containing 12-25 carbon atoms have insecticidal activity (See US. Pat. No. 3,012,932); that araliphatic isonitriles having a total of 7-12 carbon atoms exhibit biocidal activity (See British Pat. No. 994,616); and that N-lower alkyl cyanophenyl carbamates have insectil5 cidal properties (See US. Pat. No. 3,329,702). However, the present invention provides novel chemical compounds in which both the isocyano (i.e., isonitrilo) and carbamate groups are present in the same molecule, which compounds display insecticidal activity.

SUMMARY OF THE INVENTION The present invention relates to novel isocyanophenyl carbamates and to the use of these compounds in the control of insects and acarids. The compounds of 25 particular interest are those represented by the formula 1 (R L NC in which X and X are each oxygen or sulfur; R and R are each 1-1, alkyl (C -C aryl, substituted aryl, or cycloaliphatic; R is selected from the group consisting of alkyl (C -C alkoxy, allyl, methylenedioxy, haloalkyl,

2 propargyloxy and allyloxy, and mixtures thereof; 1| 1 n is an integer from 0 to 4 inclusive; and 1 c 7 30 A is phenyl or naphthyl.

2 Illustrative examples of isocyanophenyl carbamates 3 n A NC encompassed within the above described genus are:

Compound N0 Compound Structu re 1 3 I socyanophenyl-N-methyl- OCONHCH3 carbamate f I I 2 3-Isocyanophenyl-N- (4-bromo- OCONH Br phenyl) carbamate NC 3 3 Isocyanophenyl-Nphenyl OCONH@ carbamate 4. 4-IsocyanophenylN-methyl OCONHCH carbamate NC 5. 5-Isocyano-Z-methylphenylN- OCONHCH methylcarbarnate CH3 'l'ublc -(onlinllcd Compound No, Compound Structure 6. 3-Isocyanophenyl-N,N-diphenylcarbamate OCON 7. 2-Iocyanophenyl-N-methyl- OCONHCH carbamate NC 8. 3-Isocyanophenyl-N- (n-propyl) OCONH(CH2) 2 3 carbamate f 9. 3-Isocyanophenyl-N- (n-butyl) OCONH(CH2) 3 3 carbamate -1' 10 3IsocyanophenylN-ethyl OCONHCHZCH carbamate 3 11. 3-Isocyanophenyl-N-cyclohexylcarbamate OCONH l2. 2, 5-Dimethyl-4-isocyanophenyl- N-methylcarbamate CONHCH3 13 4-1socyanophenyl-N,N-dimethyl carbamate OCON (CH 2 14. 4-Isocyano-Z-methylphenyl-N methylcarbamate OCONHCH Table -(ominucd Compound No. Compound Structure OCON (CH 2 l5. 2-Isocyanophenyl-N,N-dimethylcarbamate l6. 3-Is0cyanophenyl-N,N-dimethyl- OCON(CH 2 carbamate C 17. 4-1socyano-2isopropyl5 methylphenyl-N-methyl- CONHCH3 carbamate H(CH3) 2 18. 4, S-Methylenedioxy-Z- OCONHCHs isocyanophenyl-N-methylcarbamate c l9. 5-Isocyano-l-naphthyl-N- OCONI-ICH methylcarbamate NC 20. 2-sec-Butyl-4-isocyanophenyl-Nmethylcarbamate OCONHCH3 CHCH CH g 21. 3-Eert-Butyl-4-isocyano- OCONHCH phenyl-N-methylcarbamate 3 @c (CH 3 OCONHCH 22. 3,5-Dimethyl-4-isocyano- 3 phenyl-N-methylcarbamate OCONHCH 23. 2,6-Dimethyl-4-isocyanophenyl-N-methylcarbamate Table Continued Compound No Compound Structu re 42 4-Ethyl-2isocyanophenyl-N methylcarbarnate OCONHCH 43. 2,3,5,6Tetramethyl4- isocyanophenyl-N-methylcarbamate OCONHCH N-methylcarbamate CH3 flag CH CH 44 2-Allyl-6-methyl-4-isocyanophenyl- CONHCH3 H C CH CH=CH 45. 3-Trifluoromethyl-4-isocyanophenyl- N-methylcarbamate 46. 2-Propargyloxy-4isocyanophenyl- N-methylcarbamate 47 2-Allyloxy-4-isocyanophenyl- N-methylcarbarnate As hereinbefore stated, the compounds of the present invention are useful as insecticides and acaricides.

They are conveniently applied to the locus of infestation in a variety of ways, for example, as a solution in an organic solvent, as an emulsion, as a spray, on an inert carrier such as clay, kaolin, talc, bentonite, attapulgite, or diatomaceous earth and the like, or as a formulated product in liquid or solid form. Useful organic solvents are the aromatics such as toluene, xylene, benzene, cyclohexane, and alkylated coal tar distillates, aliphatics such as naphthas and petroleum distillates, and

OCONHCH3 @ELCF OCONHCH3 OCH2-C-ECH NC OCONHCH i OCH CH=CH NC (Reaction I) NHZ nncno p-aminophenol p-formamidophenol (Reaction III) 4-formamidophenyl-N-methylcarbamate Reaction I Reaction of p-aminophenol with formic acid in aqueous solution Method A One mole of p-aminophenol is added to a large excess of 90% formic acid (4-6 moles) and heated at 8090C. for 3 to 4 hours. The reaction mixture is then permitted to cool slowly to room temperature. The resulting p-formamidophenol crystals are filtered off, washed thoroughly with water and then dried. If the product fails to crystallize, it is then poured into an icewater slurry. The solid is then filtered, washed with water and then dried.

Reaction ll Reaction of p-formamidophenol with methyl isocyanate Method A 40- Methyl isocyanate (0.25 mole) is added to a stirred mixture of the formamidophenol (0.20 mole) prepared by Reaction 1, benzene or ether (300 ml.), and triethylamine (1 ml.). The reaction mixture is heated at 40-45C. for 3-5 hours, then cooled to 12C. and filtered. If the reaction is not complete, additional methyl isocyanate is added and the reaction continued. The solid 4-formamidophenyl-N-methylcarbamate product is washed with benzene (or ether) and dried.

+ CO 2 (C H N'HCl 4-isocyanophenyl-N-methylcarbamate Reaction llll Reaction of 4-formamidophenyl-N-methylcarbamate with Phosgene Method A A solution of phosgene (0.11 mole) in methylene chloride (100 ml.) is added to a refluxing mixture of the formamido carbamate (0.1 mole), methylene chloride (133 ml.) and triethylamine (0.26 mole). Refluxing is continued for an additional 10 minutes after the addition is complete. The solvent (methylene chloride) is removed under reduced pressure maintaining the temperature below 50C. The residue is extracted with benzene and the benzene is removed under reduced pressure leaving the desired 4-isocyanophenyl-N- methylcarbamate.

Reaction 1, Method A is not suitable for aminophenols having long chain alkyl substituents, i.e., substituents greater than 4 carbon atoms in length. In the instance where a long chain alkyl aminophenol is employed in the synthesis of an isocyanophenyl carbamate, a preferred method is the following Reaction 1 Method B A stirred slurry of the aminophenol (0.2 mole), benzene (200 ml.) and 90% formic acid (0.25 mole) is heated at reflux for 4 hours. The water of reaction and that contained in the formic acid are removed by azeotropic distillation. The dry formamidophenol is now dissolved in benzene for Subsequent reaction to form the carbamate.

1n the instance where the formamidophenol is prepared according to Reaction 1, Method B, then the following procedure is employed to form the formamido carbamate Reaction 11 Method B The benzene solution of the formamidophenol is treated with triethylamine until a pH of 9 is obtained. Methyl isocyanate (10% excess or more if necessary) is added and the mixture is heated at 4045C. for 3 to 4 hours, then cooled and filtered. The precipitate of formamidocarbamate is washed with benzene and dried.

An N, N-dialkyl or N,N-diaryl substituted carbamate is prepared from a formamidophenol according to the following equation and method (Reaction 1], Method C):

OH (R @-uacno ClCONR R -)(R Reaction [1 Reaction lll Method B Phosgene (0.11 mole) is bubbled into a stirred mixture containing the formamidophenyl carbamate (0.10

.16 mole), benzene (250 ml.) and triethylamine (0.28 mole). The temperature is maintained below 15C. by means of a cooling bath. The cooling bath is removed and the stirring is continued for 1 hour. Water is added and the organic and aqueous layers are separated. The organic layer is dried and evaporated below C.

under reduced pressure to provide the desired isocyanophenyl carbamate.

Reaction lIl Method C Phosgene is passed rapidly (1-2 grams/min.) into a homogenized mixture of formamidophenyl carbamate (0.1 mole) in triethylamine (0.26 mole) and methylene chloride (300 m1.). A phosgene excess varying from 10 to 25% is generally required for complete conversion of amide to isocyano group. The progress of the reaction is followed by using an infra-red spectrophotometer (gradual disappearance of amide band with the simultaneous appearance of the isocyano band at about 2,125 emf). The reaction must be maintained on the alkaline side. Additional triethylamine may be added if necessary.

CONR R NHCHO The isocyanophenyl carbamate product is isolated by washing the reaction mixture with water, 5% aqueous hydrochloric acid and again with water. The organic layer is separated, dried over anhydrous magnesium sulfate and then concentrated under vacuum below 50C. Further purification may be accomplished by recrystallizing from benzene, petroleum ether (90C.) or a combination of both or by chromatography over silica gel.

For a more complete understanding of this invention, reference is now made to the following specific examples illustrating the preparation of the novel compounds of the present invention and their efficacy as insecticides and acaricides.

EXAMPLES 1-15A (Table 1 The following table, Table 1, summarizes the preparation of representative examples of the present TABLE 1 Rcactants and Procedure COM- POUND EXAMPLE NO AMINOPHENOL USED ISOCYANATE REACTIONS YlELD* l 1 B-Aminophenol Methyl lsocyanatc 1A, 11A, [11A 67% 2 14 2-Methyl-4-Aminophenol do. 1A. 11A, 1118 84% 3 22 3,5-Dimethyl-4-Aminophenol do. 1B, 11A, "18 95% 4 23 2,6-Dimethyl-4-Aminophcn0l do. 1B, "A, 111A 88% 5 25 2ls0propyl-4-Aminophcnol do. 18, 11B, 1118 74% 6 21 3-Tert-Butyl-4-Aminophcnol do. 1A, 11A, [11B 90% 7 l6 3-Aminophcnol Dimethylcarbamoyl lA, 11C, 1118 90% Chloride 8 15 Z-Aminophenol do. 1A, 11C, 111B 91% 9 9 3-Aminophenol n-Butylisocyanatc 1A, 11A, 1118 98% 10 i 8 3Aminophcnol nPropylisocyanatc 1A, 11A, 1118 91% l 1 1 1 3-Aminopheno1 Cyclohcxylisocyanatc 1A, 11A, 1118 93% l2 l9 S-Amino-l-Nuphthol Methyl lsocyanatc 1A, 11A, 111C 13 44 2-Mcthyl-6-Allyl-4- Methyl lsocyanatc 1A. 11A, 111C Aminophenol 14 45 3-(Trifluoromethyl)- Methyl lsocyanatc 1A, 11A, 111C 51% 4-Aminophcnol 15 46 2-Proparg \'loxy-4-Aminophcnol Methyl lsocyanate 1A. 11A, "111C 21% 15A -17 Z-Allyloxy l-Aminophenol Methyl lsocyanutc lA, l1A. jlllC 30% Yield 01' final reaction tic. 111A 17 isocyanophenyl carbamates. The Roman numerals and capital letters under the caption Reactions refer to the previously described reactions. Thus, for example, a notation M, "A, "M means Reaction l, Method A, Reaction ll, Method A, and Reaction lll, Method A.

EXAMPLES l6-74 The insecticidal and acaricidal activities of representative and typical isocyanophenyl carbamates of this invention were determined according to the following described methods.

INTRODUCTION Candidate samples were formulated by dissolving the sample in acetone containing small amounts of emulsifier. The test formulations were then diluted in water to obtain the desired active ingredient concentration.

Where solubility was a problem, the diluted test formulation was wet ball-milled.

Southern Armyworm (Pmdenz'a eridania), and Mexican Bean Beetle (Epilachna varivestis) Lima bean leaves dipped into test solutions of the respective compounds were offered to larvae of the Southern armyworm (late third instar) and the Mexican bean beetle (late second instar) for a 48-hour feeding period. Mortality data were recorded. In these tests, as in tests against all other organisms, untreated controls were included for comparative purpose.

Tables 2 and 3 summarize the activity of the indicated isocyanophenyl carbamates against Southern armyworms and Mexican bean beetles respectively. Blank spaces in these and subsequent Tables mean that no tests were conducted at the corresponding particular concentrations.

TABLE 2 Test Organism: Southern Armyworm (Prodenia eridania) Percent Mortality Application Concentration Example No. Compound No. 0.35% 0.175% ().l% 0.05% 0.0l% 0.005% 0.001%

16 38 100 0 l7 l4 1 ()0 90 40 l 8 I2 I00 100 I00 I00 l0 l) 24 100 I00 50 20 37 100 100 Hill 70 t) 2] 30 Hit) 00 (l 12 22 Hit) Hill 100 U 13 2X 10 24 25 )0 25 27 l()() [00 90 ll) 26 2! I00 l()(] 40 27 17 X0 28 26 I00 I00 l00 90 0 29 19 90 I00 20 30 4 I00 I00 40 0 3l 1 40 32 l3 80 33 I5 I00 0 34 43 40 35 45 70 Untreated 0 0 0 0 0 0 0 36 23 30 37 47 60 TABLE 3 'l'cst Organism: Mexican Bean Beetle (Epilaehnzl varivestis) Percent Mortulity Application Concentration EXAMPLE (OM- POUND NO. NO. |.07( 0.35'7/ 0. l 75% 0. W: 0.05% 0.0 l '71 0.005% 0.0017! 0.000571 38 2X 90 50 39 38 l()() 80 0 40 14 I00 I00 60 20 41 12 I00 I00 100 I00 70 0 42 24 I00 H10 100 0 43 37 100 I00 I00 60 1O 44 5 I00 30 45 30 I00 I00 I00 0 46 22 I00 I00 I00 0 47 33 50 0 48 25 I00 100 l0() 0 49 27 100 100 l00 100 90 40 50 21 I00 100 I00 100 100 30 51 20 I00 52 I7 I00 100 30 53 26 I00 I00 I00 90 50 54 19 I00 lOO 100 l ()0 70 20 55 l l 20 56 3| I00 I00 57 32 I00 60 58 2) l0 5) [H (I M) I It") lllt) [U0 (1 TABLE 3 Continued Test Organism: Mexican Bean Beetle (Epilachnu varivcstis) Percent Mortality Application Concentration EXAMPLE COM- POUND NO. NO. l.0% 0.35% 0. l 75% 01% 0.05% 0.01% 0.005% 0.00l% 0.000570 61 g 4 I 100 80 50 62 7 8O 63 100 70 64 I3 80 65 16 40 66 42 60 67 44 6O 68 45 I00 Untreated 0 0 0 O O 0 0 O l) 69 8 30 70 l0 I0 71 40 80 72 4] 20 73 36 I00 74 47 I00 80 50 30 EXAMPLES 75 170 Strawberry Mite (Tetranychus atlanticus) Excised lima beam plants were infested with 50 to 100 adults of the starawberry spider mite prior to testing. The infested plants were dipped into water dilutions of each test chemical. Treated test plants were allowed to dry and then cultured at room temperature. After 5 days, mortality counts were made. The results are noted in Table 4.

"Pa A hids aadnsasemes' Ten adult pea aphids were sprayed with representative compounds of this invention diluted to the desired concentration and transfered to similarly sprayed pea To the vermiculite substratum of potted pea seedlings there is applied 25 ml. of the candidate chemical which has been diluted in a suitable non-phytotoxic solvent. Three days after treatment the pea plants are infested with ten adult pea aphids (Macrosiphum pisi).

Diluted samples e e ppli t0 P ph and to Mortality determinations are made after 5 days.

houseflies in a contact test by means of the Waters vertical spray tower. The spray tower is operated at 10 psi and discharges about 28 ml. of material per minute through a glass atomizer. The spray descends tthrough an 8 inch stainless steel cylinder to the plant or test insects 44 inches below the atomizer.

Pea Aphid (Macrosiphum pisi) Contact Test Housefly (Musca domestica) Fifty adult houseflies were sprayed in a 2 inches high by 5 inches diameter stainless steel cage faced on top and bottom with 14 mesh screen. The insects were retained in the same cages for knockdown observations.

TABLE 4 Test Organism: Strawberry Mite (Tetranychus atlanticus) Percent Mortality Application Concentration EXAMPLE COM- POUND NO. NO. 0.35% 0.175% 0.1% 0.05% 0.0l% 0.005% 0.00l%

28 I00 86 0 76 38 lOO 71 26 77 14 lOO 0 78 I2 lOO 100 lOO 0 79 37 90 69 6 80 30 100 100 94 73 0 8] 22 100 I00 33 82 24 86 83 5 6i 84 25 100 93 21 85 l7 I00 0 86 2] 85 87 35 25 88 34 41 89 26 100 100 100 33 )0 I9 40 91 6 22 92 l l 85 93 18 53 Test Organism: Strawberry Mite (Tetranychus atlanticus) Percent Morta1ity Application Concentration EXAMPLE COM- POUN Untreated 0 0 0 O 0 0 0 0 TABLE 5 Test Organism: Pea Aphids (Macrosiphum .pisi) CONTACT TEST Percent Mortality Application Concentration EXAMPLE COM- POUN NO. NO. 1.0% 0.35% 0.175% 0.1% 0.05% 0.01% 0.005% 0.001%

1 12 33 1 13 38 100 so 20 1 14 14 100 20 12 v 100 100 100 80, 75 10 1 16 24 100 100 100 O 1 17 37 100 50 20 1 18 5 100 80 1 50 1 19 30 100 90 8O 20 22 100 100 90 0 121 28 10 122 25 100 100 100 O 123 27 10 124 21 100 60 O 125 20 90 126 17 100 100 100 O 127 34 30 128 26 100 100 0 129 19 100 100 100 60 V0 130 31 100 80 50 131 32 20 132 '18 6O 10 133 1 100 100 40 134 4 100 100 90 0 135 7 100 100 100 23 136 13 100 100 80 3 137 15 100 100 90 10 138 16 100 100 60 139 42 50 140 43 10 141 44 40 Untreated 0 0 O 0 O 0 0 O 142 10 1 40 143 23 60 144 40 100 90 10 145 41 100 60 20 146 36 100 0 147 46 10 148 47 2O SYSTEMIC TEST 149 24 1 100 80 50 150 26 9O 1 40 151 4 100 0 152 7 30 153 40 20 23 TABLE 6 24 Test Organism: Housefly (Musca domestica) Percent Mortality Application Concentration EX. COM- 0.35% 0.175% 0.1% 0.05% 0.01

POUND NO. NO. KD" Kill KD" Kill" KD" Kill" KD" Kill KD" Kill" 155 12 100 100 20 100 14 98 I! 156 14 8 90 16 62 0 2 157 30 40 96 t) 20 158 22 20 98 70 88 U 0 l) 38 0 160 5 14 X0 161 24 (l 14 162 37 0 I63 25 X 164 27 30 28 165 21 76 88 166 17 100 100 84 100 0 14 167 26 100 X0 100 76 0 2 168 19 22 169 31 100 100 92 82 4 8 I 32 (l 4 l7] 7 lot) 100 2 2 4 I8 172 l O 68 173 15 100 100 22 84 (l 4 174 16 100 100 26 70 O 2 I 13 24 96 2 l6 Untreated 0 (l 0 0 0 0 O 0 0 176 46 O 24 Percent of flies knocked down 2 hrs. after treatment application. Percent of flies killed 24 hrs. after treatment uppliculion.

EXAMPLE 177 were determined according to the following procedure utilizing cucumber seedlings infested with melon aphids.

Cucumber seeds (variety Chicago Pickling) were planted in 16 oz. plastic pots filled with potting soil and rates of 12.5 ppm and 25.0 ppm based on the weight of air dry soil in each replicate. Saran film was used to seal the soil surface of each pot to exclude compound vapors, if any, from insect infested leaf surfaces.- Treatments were replicated five times.

The treated cucumber seedlings were cultured at 68F. under artificial light until final insect counts were made. Live aphid counts were conducted on thirteen sixteenths inch diameter leaf discs removed from the first true leaf of each plant. The following Table sets forth the results obtained:

cultured in the greenhouse to the two true leaf growth 40 Average No. of Aphids/Leaf Disc Application Concentration 12.5 ppm 25.0 ppm COM- Average Insect Percent Average Insect Percent POUND NO. Count Mortality" Count Mortality 12 0.4 99.2 0.75 99.2 24 0 0 100 26 3.5 93.1 8.0 91.9 30 1.25 97.5 5.0 94.9 37 8.5 83.1 3.25 96.7 Control 50.5 98.2

" Based on the weight of air dry soil used in each replicate. Calculated as ((ontrol'Aetuall/(ontrol X 100 stage. Cucumber plants previously infested with melon aphids (Aphis gossypii) were introduced into the seedling propagation, whereupon, aphid infestation of the propagation was allowed to progress naturally until approximately 200 aphids per seedling were observed. Test treatments were applied at that time.

Each test compound was applied as a soil drench at EXAMPLE 178 To illustrate the unexpected variation in insecticidal and acarieidal activity provided by the introduction of the isocyano (i.e., NC"group into the phenyl carbamate molecule, a comparison was made between the following compounds:

CONHCH3 AND H30 CI-I(CH3) 2 3-isopropyl-S-methylphenyl-N- methylcarbamate OCONHCH NC CH(CH 3-isopropy1-5-rnethy1-4- isocyanophenyl-N-methy.l

carbamatc SOUTHERN ARMYWORM Concentration Percent Mortality ("/11 W/V) PROMECARB COMPOUND NO. 26

(H0 I00 I00 0.05 90 I00 (HH 0 I00 not tested It is apparent that Compound N0. 26 is IO times more active than PROMECARB against Southern Armyworm.

MEXICAN BEAN BEETLE Percent Mortality CONCENTRATION W/V) PROMECARB COMPOUND NO. 26

0.10 100 I00 0.05 I00 I00 0.01 I00 I00 0.005 I00 90 0.00l I00 50 0.0005 80 0.00025 30 not tested Against Mexican Bean Beetle, PROMECARB is about five to times more active than COMPOUND NO. 26.

STRAWBERRY MITE Percent Mortality CONCENTRATION W/V) PROMECARB COMPOUND NO. 26

0.10 I00 I00 0.05 27 100 0.01 I00 0.005 95 0.00l 33 not tested COMPOUND NO. 26

COMPOUND NO. 26 is approximately 20 to times more active than PROMECARB against Strawberry Mite.

PEA API-IID CONCENTRATION Percent Mortality W/V) PROMECARB: COMPOUND N0. 26

Contact Systemic Contact Systemic 0.10 I00 0 I00 0.05 50 I00 40 0.01 0

" not lcxlctl COMPOUND NO. 26 is more active (approximately twice) than PROMECARB against Pea Aphid when both compounds are applied directly to the test organism. COMPOUND NO. 26 exhibits systemic activity against Pea Aphid while PROMECARB is inactive at the rates tested.

HOUSEFLY Percent Mortality CONCENTRATION PROMECARB COMPOUND No.

(% W/V) Knock- Kill Knock- Kill down down 0.10 I00 I00 I00 80 0.05 I00 I00 76 0.0 l 80 28 0 2 PROMECARB is more effective than COMPOUND NO. 26 against Housefly.

The foregoing results demonstrate that isocyanophenyl carbamates, when compared with the corresponding phenyl carbamates display unpredictably greater activity against certain insect and acarid species but less activity against others.

EXAMPLE 179 To determine the difference in insecticidal and acaricidal activity between cyanophenyl carbamates and the isocyanophenyl carbamates, the following compounds were compared.

the

27 28 4-cyanopheny1-N-methy1carbamate 4-isocyanophenyl-N-methy1- carbamate OCONHCH CQNHCH3 COMPOUND A COMPOUND NO 4 and 2-cyanopheny1-N-methylcarbamate 2-isocyanophenyl-N-methylcarbamate I vs. NC

COMPOUND B COMPOUND NO. 7

The species against which activity was tested were: HOUSEFLY (M. doniestica) SOUTHERN ARMYWORM (P. eridania) MEXICAN BEAN BEETLE (E. varivestis) PEA APHIDS (M. pisi) STRAWBERRY MITES (T. atlanticus) These tests demonstrate that COMPOUND NO. 4, when compared to its cyano-counterpart (COM- POUND A) is vastly more active against the Southern Armyworm. However, it is noted that .both COM- POUND B and COMPOUND NO. 7 are relatively inactive against this organism.

The results were as indicated by the following Tables: MEXICAN BEAN BEETLE HOUSEFLY 30 Percent Mortality Percent Mortality CONCEN' TRATlON COM COM- COM- COMPOUND POUND POUND POUND CONCENTRATION COMPOUND A COMPOUND NO. A NO 4 I B No 7 w/v) Knock- Kill Knock- Kill 838 a {88 3 g down down k a 0.35 0 0 50 0 6 40 Not Tested Not Tested COMPOUND NO. 4 1s markedly more active against Mexican Bean Beetles than COMPOUND A. There ap- CONCENTRA'HON COMPOUND B COMPOUND 7 pears to be very little difference in activity between w/v) Knock- Kill KnOCk- Kill COMPOUND B and COMPOUND down down 0.35 100 100 PEA APHIDS 0.10 100 100 2 2 0.05 100 100 4 18 I 001 O 0 m x Percent Mortallty Tamed CONCENTRATION COMPOUND A COMPOUND NO. 4

W/V) Contact Systemic Contact Systemic ln general, against housefltes, the cyanophenyl carbamates display greater activity than the corresponding 8-? 6 T :88 8 isocyanophenyl carbamates. 90 0.0] 0 SOUTHERN ARMYWORM Not Tested Percent Mortality CONCEN- 6O TRATION COMPOUND CONCENTRATION COMPOUND B COMPOUND NO. 7

POUND POUND POUND A NO- 4 B NO- 7 W/V) Contact Systemic Contact Systemic Not Tested Not Tested STRAWBERRY MITES Percent Mortality CONCEN- TRATION COM- COM- COM- COMPOUND POUND POUND POUND W/V) A NO. 4 B NO. 7

Not Tested It is seen that COMPOUND NO. 4 displays significantly greater activity against Strawberry Mites than COMPOUND A. COMPOUND B appears to have slightly greater activity than COMPOUND NO. 7.

Thus, given the known activity of the cyanophenyl carbamates, it is evident that the corresponding isocyanophenyl carbamates differ markedly in their activities against various species.

The conclusion that can be drawn from the foregoing tests of Examples 172 and 173 is that insecticidal and acaricidal activity cannot be predicted by an inspection of chemical structure, even where a similar compound is known to exhibit a specific activity.

As hereinbefore stated, the isocyanophenyl carbamates of the present invention are broadly effective as insecticides and acaricides. It should be understood, however, that each particular compound of the present isocyanophenyl carbamate genus, although exhibiting insecticidal and acaricidal activity as indicated by the foregoing examples, may not be effective against each and every insect and acarid species. It is recognized in the pesticidal art that broad spectrum insecticides are not necessarily active against every insect species. Therefore, for the sake of brevity, test data indicating no apparent activity against a particular species have not been included in the examples. This may be illustrated by reference to Compound No. 27, which was found to be highly active against Southern Armyworm and Mexican Bean Beetle, and slightly active against Housefly and Pea Aphid. However, it was inactive against Strawberry Mite and was therefore not included in the data for this particular species. On the other hand, Compound No. 28 was found to be moderately active against Strawberry Mite and Mexican Bean Beetle, Southern active against Suthern Armyworm and Pea Aphid, but inactive against Housefly. Therefore, to keep the tables as brief as possible, no data for Housefly was entered for Compound No. 28.

What is claimed is: 1. lsocyanophenyl carbamates having the general formula in which R, and R are each hydrogen, alkyl (C -C R is alkyl (C,-C and mixtures thereof; and n is an integer from 1 to 3 inclusive.

2. lsocyanophenyl carbamates according to claim 1 wherein R is H;

R2 is R is CH 3. lsocyanophenyl carbamates according to claim 1 wherein R is H;

R is CH R is CH, and isopropyl;

n is 2-3.

4. lsocyanophenyl carbamates according to claim 1 wherein R is H;

R is CH R is isopropyl;

and n is 2.

5. methylcarbamate.

6. methylcarbamate.

7. methylcarbamate.

8. methylcarbamate.

9. 3-methyl-4-isocyanophenyl-N-methylcarbamate.

10. 3-isopropyl-5-methyl-4-isocyanophenyl-N- methylcarbamate.

2,5 -dimethyl-4-isocyanophenyl-N- 2,3-dimethyl-4-isocyanophenyl-N- 3,5-diisopropyl-4-isocyanophenyl-N- 2,3 ,5-trimethyl-4-isocyanophenyl-N- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,862,976 Dated January 28, 1975 Inventor(s) DAVID L BOOTH It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

1. Column 13, under "Reaction II The caption should be "Method A" and not "Method A 40 2. Table 5, Example 112, Compound 33 The number "2Q" should appear under 0.1%, and the number "Q" should appear under 0.05%.

3. Column 30, line 4:

(1) Delete "Southern", first occurrence,

and substitute therefor "slightly",-

(2) Correct the spelling of "Suthern" to "Southern".

Signed and sealed this 22nd day of April 1975.

(SEAL) Attest n C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks FORM PO-IOSO (10-69) uscoMM-DC 60376-P60 u. s. covnnmzmmum-me omcs ins o-asc-as-s, 

2. Isocyanophenyl carbamates according to claim 1 wherein R1 is H; R2 is CH3; R3 is CH3.
 3. Isocyanophenyl carbamates according to claim 1 wherein R1 is H; R2 is CH3; R3 is CH3 and isopropyl; n is 2-3.
 4. Isocyanophenyl carbamates according to claim 1 wherein R1 is H; R2 is CH3; R3 is isopropyl; and n is
 2. 5. 2,5-dimethyl-4-isocyanophenyl-N-methylcarbamate.
 6. 2,3-dimethyl-4-isocyanophenyl-N-methylcarbamate.
 7. 3,5-diisopropyl-4-isocyanophenyl-N-methylcarbamate.
 8. 2,3,5-trimethyl-4-isocyanophenyl-N-methylcarbamate.
 9. 3-methyl-4-isocyanophenyl-N-methylcarbamate.
 10. 3-isopropyl-5-methyl-4-isocyanophenyl-N-methylcarbamate. 